Carbenoid Chemistry

Carbenoids – compounds with a leaving group directly bound at a metalated carbon atom – are unique organometallic reagents. Due to their constitution with a they exhibit an ambiphilic character and thus versatile reactivities. Despite these unique features applications of carbenoids are still rather limited. This is due to their high reactivity and often thermal lability, which hamber controlled and selective applications.
Our research project aims at controlling the carbenoid stability by adjustment of the electronic and steric properties as well as the coordination/ solvation of the metal. Here, we are interested in uncovering structure-stability relationships in order to predict and fully control the reactivity of the carbenoids. The reactivity control will then be used to develop new and selective applications beyond classical cyclopropanation reactions.

Recent discoveries in our group have for example shown that changing the M/X combination is an powerful tool for stability and reactivity control. As such, potassium and sodium carbenoids turned out to be more stable than their lithium congners and could thus be used as selective carbene transfer reagents (Angew. Chem. 2016). On the other hand, we demonstrated that stabilized carbenoids can be used in selective B-H activation reactions (Chem. Eur. J. 2013) or in the dehydrocoupling of phosphines to form diphosphines (JACS 2014), a reactivity which hasn’t been observed before in carbenoid chemistry.